Reduction of Nitroaromatic Compounds on Supported Gold Nanoparticles by Visible and Ultraviolet Light

Zhu, Hongkai; Ke, Xuebin; Yang, Xin; Sarina, Sarina; Liu, Hongwei

doi:10.1002/anie.201003908

Cited by 398 publications

(274 citation statements)

References 30 publications

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“…3 While the design of heterogeneous photocatalysts has focused largely on semiconducting light absorbers, 4,5 it has recently been demonstrated that metallic nanostructures offer unique characteristics for facilitating photocatalytic reactions. [6][7][8][9] Strong light absorption through the excitation of localized surface plasmons on plasmonic metal nanostructures 10 comprised of Au, [11][12][13] Ag, [14][15][16] Cu, 17 or Al, 18 has been shown to drive photocatalytic processes through the excitation and transient transfer of energetic, or hot, carriers to adsorbates. [19][20][21][22][23][24] However, there is limited evidence that the energies of hot carriers in plasmonic nanostructures can be selectively tailored to target specific catalytic reaction pathways, 25,26 and plasmonic nanostructures are optimal catalysts for only a very few 4 relevant industrial chemical processes.…”

Section: Main Textmentioning

confidence: 99%

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Li¹,

Hogan²,

et al. 2017

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Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction.Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g. Ag) is coupled to the catalytic properties of the non-plasmonic metal nanoparticle (e.g. Pt) to enable chemical transformations. With an eye towards sustainable solar driven photocatalysis we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 where the plasmonic nanoparticle is the antenna and the catalytic particle, which can be interchanged based on desired reactivity, is the reactor. In an antenna-reactor complex, the local field induced by the photoexcited antenna particle drives a "forced" plasmon in the nonplasmonic, catalytic nanoparticle: this forced plasmon can serve as a direct source of hot carriers in the catalytic particle to drive chemical processes without the need for charge transfer between the antenna and the reactor components of the nanocomplex. In the initial demonstrations of antenna-reactor coupling, however, the optimal geometric configuration of the constituent materials to maximize photocatalytic performance was not addressed. Furthermore, while it is relatively straightforward to conclude that localizing a plasmonic particle near a non-plasmonic catalytic particle will enhance light absorption in the non-plasmonic particle, it is not clear how this translates to enhanced photocatalysis in the light-limited regime, where all photons must be utilized in a 3-D packed bed of catalytic particles. Optimizing photocatalytic complexes for highest efficiency photon management in the light-limited regime is of critical importance for further development of this approach.In the work reported here, a series of antenna-reactor complexes consisting of core@shell/satellite (Ag@SiO 2 /Pt) heterostructures with varying Ag core diameter (12,25,50 and 100 nm) were synthesized and their photocatalytic properties for the kinetically well-defined CO oxidation reaction were quantitatively compared. Rigorous quantum yield measurements in the light-limited regime demonstrate that for heterostructures with Ag nanoparticles (Ag NPs) in an intermediate size range of 25 and 50 nm diameter, plasmon-enhanced photocatalytic performance was observed at rates more than four times larger than for either smaller (12 nm diameter) or larger (100 nm diameter) Ag particles. Using optical and Monte Carlo simulations, it was shown that if the Ag NPs were too large, the heterostructures scattered light out of the catalyst bed, reducing photocatalytic reactivity. If the Ag NPs were too small, l...

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Section: Main Textmentioning

confidence: 99%

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Li¹,

Hogan²,

et al. 2017

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“…Later, Zhu et al using a photocatalytic reaction with Au/ZrO 2 as catalyst, in alkaline media (KOH) and room temperature, have reported high nitrocompounds conversions with moderate to good yields to symmetric azocompounds [11] . However it should be noticed that the ratio of solvent to reactant in this process is 392/3 mmol.…”

Section: Introductionmentioning

confidence: 99%

Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step

Combita

Concepción

Corma

2014

Journal of Catalysis

102

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One step selective hydrogenation of nitroaromatics to obtain symmetric azocompounds with high yields has been performed with a gold supported on cerium oxide catalysts. Au/TiO 2 and Au/CeO 2 catalysts direct the reaction by two different pathways and with different selectivities. In situ FTIR studies reveal that the surface concentration of the intermediate nitrosobenzene is decisive in directing the reaction trough the different reaction pathways. In this way, while on Au/TiO 2 a fast hydrogenation of the nitrosobenzene intermediate leads to a low surface concentration of the nitrosocompound, on Au/CeO 2 nitrosobenzene is more stabilized on the catalyst surface leading to a lower hydrogenation and a higher coupling rate, resulting in high selectivities to azobenzene. On Au/CeO 2 the relative weak adsorption of the azo with respect to the azoxycompound on the catalyst surface, avoids the consecutive hydrogenation of azocompounds to the corresponding anilines until all the azoxy has been consumed. Asymmetric azobenzenes have also been obtained with very high yields on TiO 2 , through the Mills reaction.

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“…To explore the capability of SiO 2 /Au NPs to enhance the sensitivity of the electrode towards NB via surface absorption by silica and reduction at Au cores [30][31][32], CV studies were performed by incubating SiO 2 /Au NPs-modified electrode in 0.5 M NaCl electrolyte solution containing different amounts of 0.01 mM NB.…”

Section: Electrochemical Detectionmentioning

confidence: 99%

Sensing behavior of silica-coated Au nanoparticles towards nitrobenzene

et al. 2012

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In the present work, we report silica-stabilized gold nanoparticles (SiO 2 /Au NPs) as a wide-range sensitive sensing material towards nitrobenzene (NB). Surface hydroxyl groups of silica selectively form Meisenheimer complex with electron-deficient aromatic ring of NB and facilitate its immobilization and subsequent catalytic reduction by Au cores. Silica-coated Au NPs were synthesized and characterized for their chemical, morphological, structural, and optical properties. SiO 2 /Au NPs-modified electrodes were characterized with impedometric and cyclic voltammetric electrochemical techniques. SiO 2 /Au NPs are found to have a higher optical detection window of range, 0.1 M to 1 μM and a lower electrochemical detection window of range, 10 −4 to 2.5×10 −2 mM with a detection limit of 12.3 ppb. A significant enhancement in cathodic peak current, C 1 , and sensitivity (102 μA/mM) was observed with modified electrode relative to bare and silicamodified electrodes. The I P was found to be linearly corelated to NB concentration (R 2 00.985). The interference of cationic and anionic species on sensor sensitivity was also studied. Selectivity in the present sensing system may be further improved by modifying silica with specific functional moieties.

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Reduction of Nitroaromatic Compounds on Supported Gold Nanoparticles by Visible and Ultraviolet Light

Cited by 398 publications

References 30 publications

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step

Sensing behavior of silica-coated Au nanoparticles towards nitrobenzene

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